Yellow to red mordant dyestuffs and process of making same.



UNIT D STATES PATENT OFFICE.

ERNST BODMER AND-Q/JEIARLES DEQLAIHAVRPE, OF BAsEL, SWITZERLAND, AssIGNoRs TO DYE woRKsroR R Y L. DURAND, HUGUENIN & 00., or BASE-L, SWITZERLAND.

YELLOW To RnnMonDaN r DYESTUFFS AND PROCESS or MAKING SAME.

No Drawing.

To all whom it mag/concern. I

7 Be it known that we, ERNST B'ODMER and CHARLES DE LA HARP'E both chemists, citizens of the Swiss Republic,-and residents of Inordante'd and mordanted. fiber.

-Basel, Switzerland, haveinvented new Yello'wto Red Mordant Dyestuffs and a Process of Making Same, of which the following.

is a full, clear, and exact specification.

Nitrated rhodols have not-hitherto been known.- g

' Bythe present invention a whole series. of

valuabledycs'tufi's' can be obtained by treat; --ing rhodols with 'hitratingf" agents and transforming the'nitro-rhodols. thus obtained into alkali metal salts.-

. 'This process is applicableto the rhodols .whi'ch are derived front phthalic acidandresorcin and have the general formula;

wherein R stands for one or' two alkyl, aryl -or aralkyl groups, while in X 'asubstituent such'as, for instance, (10011, or 'SO H'may be present.

The dye'stufi' to be nit-rated is most simply dissolved in sulfuricacid and the nece ary duced are, likev the-dyestufis'ffrom which they are derived' of the analogous, notmtrated rhodols, inordant dyestuffs as shown by. the difference of their dyein gs on, not Their tints on chrome-mordanted fiber vary from yellow to reil, In distinctionfrom the cor Specification of Letters Patent.

"A plication filed July 8, 1912. Serial 'N0.'7O8,237.

' Patented Mar.11,1 913.

esponding not nitrate d rhodols, the intro;-

rhodols dye the fiber more yellowish tints.

Their acid character, namely that of the not sulfonated but only carboxylated compounds, marked; their solubility in alka- 'lis is in consequence enhanced. Certain properties-of fastness are favorably affected by the entry of'the nitro group, such as the.

fastness to light of the dyeings with chrome mordants on wool, which is much better than that of the corresponding not'nitrated rhodols.

' The new, dyestuflsare in'their serviceable form, that is-to say in thejform of'alkali metal salts brown to red powders, which are easily. soluble-in water and'fror'n thesesolut'ion's the corresponding acid nitrorhodols are precipitated by adding'acid. r

- Some of thenotsulfonated nitro-rhodols may be sulfonated for-the P rpose of in creasing their solubility under certain conditions; obviously, those which contain a ben'zyl or a phen'yl residue in the amino group are particularly easily sulfonated.

' The invention is illustnated/by the follow- H 'in%exampl es, the parts by weight:

xample I; 13.9 'parts 'of diamethylrho dols ulfonic acid (free acid of the dyestufl from dimethylamino-meta-oxy-benzoylbenzoie .acid and resorc'in. disulfonic acid, obtained as prescribed in Example II'of specification of the United States Letters Patent No. 1002825 dated September 1911 are dissolved in 4 times their weight of concentrated sulfuric acid atordinary temperature. While stirring and cooling there is added gradually a quantity of'a mixture of sulfuric acid and nitric acid, corresponding with 6.3 parts of nitric acid, for-instance 14.3 parts of such'a mixture containing 4 1 per cent. of HNO sufficient for a mononitro derivative. The nitration is completed by allowing the mixtureto stand for several days at the ordinary temperature or by heating fora 'shorttimeat 70 C.; when free nitricacid can no longer be detected in the mass, the latter is poured into icewater, the dyestufi which separates is filtered and is converted into an easily soluble alkali metal salt. The ayaaa isdistinguished from the parent dyestuif-by a more yellow tint. It dissolves in concentrated sulfuric acid with a citron yellow color turning to yellowish red,-on addition of water. Its solutions in dilute alkali are yellowish red with.- a 7 green: fluorescence. .Itdyes unmordanted wool .redv orange and chrome-mordanted wool orange-red tints.

Example-II: 10,3 parts of dimethylrhodolcarboxylic acid'(dyestufl' from dimethylamino meta-:oxy -benzoylbenzoic acid and B-resorc lic acid), or an equivalent quantity of. anot-er dye'stufi obtained, from an N- substitution derivative of amino-meta-oxybenzoylbenzoic acid and fi-resorcylic acid,

are dissolzv'ed in 4 times thequantity of sul furic acid mono'hydratei and there isadded gradually while stirringand =cooling1a quantity of a mixture ofnitric acid and sulfuric acid correspondingwith 6.3 parts of nitric acid, for instance 18, parts of such a mixture containing 35 per cent. HNQ,

15.3 per cent. SO and 49.7 per-cent, H,SO,.-

The mass is allowed to stand for some time or gently. heated for a short time until freenitric acid can no longer be detected. The dyestufi separates when the mass is poured into ice-water; it is'dissolved in hot sodium acetate solution, in which it is much more solublethan the parent dyestuif, and'is precipitated again from. the solution by adding acid. The product is thendissolved in analkali and salted out. The dyestufi thus obtained in the form of a red .powder is distinguished from-the parent dyestuif by, in addition to its more yellow tint, a considerably increased fastne'ss' tolight of its dye-f ings on chromed wool. It maybe dyed on wool with chrome 'mordants by the one.- bath or so-called American process (that is to say, the dyestufl' and 'mordant being in the dye-bath from the beginning) and also by after-chroming. It disso'lve's in concentratedsulfuric acidto yellowsolution becoming yellowish red on addition of water. Indilute alkalis it dissolves to yellowish red solutions of a green fluorescence. It dyes unmor'd'an-ted woolorange and chrome-. mordanted wool red tints.

Example III: 49.3 parts of the dyestu'fi' from ethyl-benzyl-amino-meta-oxybenzoylbenzoic acid andB-resorcylic acid .are dissolved in 4 times their weight of sulfuric acid monohydrate and. 36 parts of a mixture of nitric acid and sulfuric acid containing 35 per cent.. of HNO,, corresponding with 12.6 parts of nitric acid, are gradually added while cooling and stirring; The treatment and the finishing operation are analogous to those described in Example II.

The dyestuif thus obtained dyes unmordanted wool yellow and chrome-mordanted wool brown yellow tintsfast to iulling and light,

solution of a rhodol whereas the parent dyestufi yields a blui h red tint. It dissolves in concentrated sulfuric acid with a yellow-brown coloration I facture of yellow to red mord'ant dyestuffs,

which consists in treating a sulfuric. acid dfyestufi' with a nitrating agent and trans orming the product thus obtained into an alkali metal salt.

V 3. The described process for the manuii'ac-v ture of orange red to red dyestufi's, which consists in .treating a rhodol dyestufi'. de-

rived from a 'dia'lkylamino-mieta-oxybenzoylbenzoic acid with a nitrating agent in a suitable medium and transforming the product thus obtained into an alkalimetal salt.

4 The described'prooessfor the manufacture of orange redto red dyestuffs, which from a dialkyl-amino-,meta-oxybenzoylben- 'zoic acid and B-resorcylic acid with anitrat- I ing agentin a suitable medium and trans- "forming the product thusobtained into an alkali metal salt.

As new products, the described nitra't'ed rhodol dyestufi'sin the form of their alkali metal salts constituting in dry state brown .to, red powders,'which are easily soluble in water and precipitated from these solutions by addition of an acid, dyeing chrome mor-' danted fibers yellow to red tints, whichare more yellowish and faster to light than those obtained with the corresponding nonn'i-tratedrhodol 'dyestufis, dissolving in concentrated sulfuric acidwithyellow ,to yelconsists in treating a rhodol dyestufi derived low-brown coloration becoming yellowish red to'brightyellow-brown on addition of water and dissolving in dilute ,alkalis with yellowish red to yellow-brown coloration;

6. As a new. article of manufacture the described nitrated rhodol dyestu'fi' resulting from the nitration of the 'dyestufi" in the form'of alkali'metal salts derived fromdimethyl-amino-meta-oxybenzoylbenzoic acid and B-resorcylic'a cid and the transformation of the nitro derivative into an alkali metal salt, which constitutes in dry state a red powder easily soluble in water and can be precipitated from these'solutions b addition of an acid, dyes chrome mordante fibers red tints, which are more yellow and faster tolight than those obtained with the corresponding non-nitrated rhodol dyestuff, dissolves in concentrated sulfuric acid with yellow color- 1912, in the presence of two subscribing witation turning to yellowish red on addition nesses,

1 ERNST BODMER.

of Water and dissolves in dilute alkalis to yellowish red solutions of green fiu0res- CHARLES DE LA HARPE.

\Vitnesses cence.

In Witness whereof We have hereunto G120. GIFFORD,

AMAND RE'm'ERY.

signed our names this 24th day of June, 

